JPH023817B2 - - Google Patents

Description

[Detailed description of the invention]

Background of the Invention (Technical Field) The present invention relates to a flame-retardant acrylonitrile-butadiene-styrene copolymer containing bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether. . (Prior art) Acrylonitrile-butadiene-styrene (ABS) thermoplastic resin has a good balance of physical and mechanical properties such as abuse resistance, heat resistance, moldability, stain resistance, chemical resistance, and surface hardness. It is. Because of its good properties and reasonable price, it has been selected and used for a wide range of applications. The resin is used by phone and car manufacturers that require high impact resistant materials. Port manufacturers take advantage of this resin's high strength-to-weight ratio and good high-temperature deep drawing properties. travel bags, electrical appliances,
Manufacturers of sporting goods, safety equipment, and toys take advantage of the resin's light weight, flexibility, and high impact resistance. ABS resin is acrylonitrile, butadiene,
and derived from styrene. The general chemical structure of these resins is represented by the following formula.

【formula】

【formula】

where x, y and z (which may be the same or different values) are from about 10 to about 1500. Typical ABS
Some examples of resin properties can be found in the Mc Graw-Hill Book by Charles A. Harpar.
“Handbook of
plastics and Elastomers” No. 1-66, 1-66,
It is described on pages 1-68. These pages are incorporated herein by reference. ABS resin is used for office machines, construction parts, television parts,
Widely used by manufacturers of standard products. For many of these applications, ABS resin must be flame retardant. Many flame retardants are known in the prior art. Some of the major known documents describing these flame retardants are German Patent No. 2731817 (describing bromobisphenol flame retardants) and Japanese Patent Application Publication No. 51-117737. (described for a copolymer derived from bromobisphenol A used in flame-retardant polyolefin),
and Japanese Patent Application Publication No. 49-20155 (bromoalkyl ether of polybrominated bisphenol A used in flame-retardant polyolefins). Japanese Patent Application Publication No. 51-73548 discloses a thermoplastic polymer containing a halogenated bisphenylene ether flame retardant. Among the many flame retardants included in the broad general disclosure of these documents are the compounds used in the compositions claimed in this application. However, there is no description of flame-retardant ABS resins in the literature, nor is there any description of the remarkable compatibility of these flame retardants with ABS resins or the effect of improving impact resistance. SUMMARY OF THE INVENTION The objects, advantages and features of the present invention are about 5 to about 35% by weight of bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether and preferably about 1 to about 35% by weight of bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether. about 10
This is achieved by a flame retardant acrylonitrile-butadiene-styrene composition containing % by weight of an accelerator, preferably antimony trioxide. The method feature of the present invention is that about 5 to about 35% by weight of bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A is added to the ABS resin.
ether and preferably about 1 to about 10% by weight
A flame retardant ABS resin is obtained by mixing an accelerator, preferably antimony trioxide. Detailed Description of the Invention The present invention provides flame retardancy to ABS resin and bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether [also known as Bis(2,4,6-tribromophenoxyethyl)ether of tetrabromobisphenol A, or bis(ethoxy-
An ABS resin composition containing 2,4,6-tribromophenyl)tetrabromobisphenol A ether is provided. The compound of the present invention is produced by the following reaction scheme. In the formula, X is selected from the group consisting of fluorine, chlorine, bromine and iodine. In a first embodiment of the process, 2-haloethyl-2,4,6-tribromophenyl ether is prepared separately and then combined with base and tetrabromobisphenol A (also known as 4,4' isopropylidene). -2,2′,6,6′-tetrabromodiphenol)
react with. In this embodiment, 2-haloethyl-2,4,6-tribromophenyl ether is produced by reacting 2,4,6-tribromophenol and dihalogenated ethylene according to the following reaction scheme. . In this reaction, about 1 to about 10 moles of dihalogenated ethylene are used per mole of tribromophenol. Preferably, the reaction time is about 30 to about 600 minutes. More preferably, the reaction time is from about 60 to about 300 minutes, and most preferably from about 60 to about 180 minutes. The reaction is preferably carried out under normal pressure, but may also be carried out under increased pressure or reduced pressure. In the method of the present invention, 2 moles of 2-haloethyl-2,4,6-tribromophenyl ether are charged to a reactor together with a base and tetrabromobisphenol A per mole of tetrabromobisphenol A. In a second alternative and preferred embodiment of the invention for preparing the present compounds, the above-described tribromophenol and dihalogenated ethylene are charged to a reactor together with a base to produce 2-haloethyl-2,4,6-tribromophenol. Phenyl ether A is produced in situ and reacted with a base to produce tetrabromobisphenol A. In this second embodiment, about 2 to about 15 moles of the tribromophenol are charged to the reactor per mole of tetrabromobisphenol A. It is preferred to use nearly stoichiometric amounts of tribromophenol. In this second embodiment, from about 1 to about 10 moles of dihalogenated ethylene are used per mole of tribromophenol. It is more preferred to use about 2 to about 4 moles of dihalogenated ethylene per mole of tribromophenol, and most preferred to use about 3 moles of dihalogenated ethylene per mole of tribromophenol. In this second embodiment, the reaction time for 2-haloethyl-2,4,6-tribromophenyl ether formation is from about 30 to about 600 minutes.
The reaction time is preferably about 60 to about 300 minutes, and about 60 minutes.
and about 180 minutes is most preferred. The reaction is generally carried out at normal pressure, but may also be carried out under increased pressure or reduced pressure. In a preferred embodiment, excess ethylene dibromide is removed by vacuum distillation to 2-haloethyl-
Separate from 2,4,6-tribromophenyl ether. The reaction conditions for the first and second embodiments are almost the same once the 2-haloethyl-2,4,6-tribromophenyl ether is formed. Tetrabromobisphenol A, 2-haloethyl-2,4,6-tribromophenyl ether, and the base are reacted at a temperature of about 60 to 200°C for about 30 to about 300 minutes. In a preferred embodiment, a reaction temperature of about 125 to about 175°C is used for about 60 to about 180 minutes. Additionally, a more preferred embodiment uses a reaction temperature of about 150°C for about 120 minutes. The reaction is carried out at normal pressure, but may also be carried out under increased pressure or reduced pressure. At least about 1 mole of inorganic base per mole of tetrabromobisphenol A can be used in the process of the present invention to produce the desired flame retardant compound. In this process, it is preferred to use about 1.0 to about 2.0 moles of base per mole of tetrabromobisphenol A. metal carbonates consisting of alkali metals or alkaline earth metals selected from the first and second columns of the periodic table;
Preference is given to using a base selected from the group consisting of metal hydroxides or metal oxides. periodic table 1
Preferred alkali metals in the column are lithium, sodium, potassium, and rubidium, with sodium,
Potassium is particularly preferred. Preferred alkaline earth metals from column 2 of the periodic table are magnesium, calcium, strontium, and barium. Carbonates of alkali metals give very good results;
Soda carbonate is one preferred base. It is preferred to react tetrabromobisphenol A, 2-haloethyl-2,4,6-tribromophenyl ether and a base in the presence of an organic solvent. However, the reaction can also be carried out without an organic solvent. When an organic solvent is used, one having a boiling point of about 120° C. or higher is preferred.
For illustration, some suitable organic solvents include non-closed ring aromatic compounds such as xylene, ethylbenzene, kyumene, styrene, dibenzyl, cymenisopropyltoluene, isocymene, monobromobenzene, dichlorobenzene; Lower halogenated alkenes such as ethane chloride, ethylene tetrachloride, and carbon atoms 1 to 6
lower halogenated alkylenes; aliphatic alcohols with about 5 to about 15 carbon atoms, such as methyl amyl alcohol, octyl alcohol, and 2-ethyl butanol; about 6 carbon atoms, such as benzyl alcohol;
to about 15 aromatic alcohols; dihydric aliphatic alcohols having about 1 to 10 carbon atoms such as ethylene glycol and propylene glycol; methyl butyl ketone, methyl amyl ketone, butylone, mesityl oxide, phenyl methyl ketone, etc. Ketones having at least about 5 carbon atoms; ethers having from about 3 to about 15 carbon atoms, such as monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol, monobutyl ether of diethylene glycol diethylene glycol, monoethyl ether of diethylene glycol; Types: amyl formate, hexaline formate, hexaline acetate, heptaline formate, heptaline acetate, n-butyl acetate, methylamyl acetate, octyl acetate, 2-ethylbutyl acetate, acetate ester of methylcyclohexanol, benzyl acetate, ethylene glycol monoacetate, Ethers having about 3 to about 15 carbon atoms such as ethylene glycol diacetate, n-butyl propionate, amyl propionate, ethyl butyrate, n-butyl butyrate, ethyl hydroxyisobutyrate, isobutyl lactate, methylcyclohexanol lactate; dimethylformamide , dimethyl sulfoxide; and other known organic solvents having a boiling point of 120° C. or higher, but are not limited thereto. In another preferred embodiment, tetrabromobisphenol A and 2-haloethyl-2,
4,6-tribromophenyl ether and a base can be reacted in the presence of water. When water is used as a solvent, it is preferred to carry out the reaction in the presence of a phase transfer catalyst. Any known phase transfer catalyst can be used. The novel flame retardant ABS composition of the present invention has a
and about 35% by weight of bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether. Preferably, the composition contains about 10 to about 25% by weight of the ether. The flame retardant ABS compositions of the present invention may contain from about 1 to about 10% by weight of an accelerator. Known accelerators can be used in the compositions of the present invention. Some of these accelerators include, for example, oxides, halides, antimony acid chloride, antimony chloride, antimony oxide, stannic oxide, arsenous acid, arsenic chloride, of antimony, arsenic, arsenic, tin, lead, and germanium. , etc. These are oxides and chlorides of metals in Group A and Group A of the periodic table. Other known promoters are organic and inorganic compounds of phosphorus, nitrogen, boron, and sulfur, such as triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, tin sulfide, etc., which are also suitable promoters. It is a drug. oxides and halides of titanium, vanadium, chromium and magnesium,
and hydrates of these compounds can also be used as accelerators. These include, for example, titanium dioxide, titanium chloride, vanadium pentoxide, chromic bromide, manganous oxide, molybdenum trioxide, ammonium molybdate, stannous oxide hydrate, lead oxide hydrate, and combinations thereof. are available. A large number of organic and inorganic antimony compounds are useful as promoters. Namely, antimony sulfide, sodium antimonite, potassium antimonite, antimony butyrate, antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisate, antimony substituent. acid tris(n-octyl) ester, antimonite tris(2-ethylhexyl) ester, antimonite tribenzyl ester, antimonite trimethylolpropane ester, antimonite pentaerythritol ester, antimonite glycerin ester, and ( Compounds that produce antimony oxide upon decomposition (such as combustion) are known as accelerators. Preferred accelerators are oxides of antimony, arsenic, and pyrolead. A more preferred promoter is an oxide of antimony. The most preferred accelerator is antimony trioxide. It is also within the scope of the invention to use other materials in the compositions of the invention if it is desired to obtain a particular end result. Such other substances are not particularly limited, but include adhesive strength agents,
antioxidants, antistatic agents, fungicides, colorants, other flame retardants (in addition to the non-condensation product-based flame retardants mentioned herein), heat stabilizers, light stabilizers,
Fillers, reinforcements, and e.g. Modern Plastics
These are other known substances described in Encyclopedia Vol. 52, No. 10A, Matsuku Grow-Hill Publishing, New York (1975), etc. The Encyclopedia is incorporated in its entirety into this disclosure. The aforementioned materials that may be used in the compositions of the present invention may be used in amounts that do not significantly adversely affect the properties of the compositions. That is, the amount ranges from zero percent relative to the total weight of the composition to a content such that the composition is still classified as a plastic. Generally the amount is between zero and 80%. A preferred flame retardant additive that can be used in the claimed compositions is bis(2,4,6-
In addition to tribromophenoxyethyl) tetrabromobisphenol A ether, it also contains an accelerator. Such ethers contain at least 50% by weight of this preferred flame retardant additive. Most preferably, the ether contains at least 70% by weight flame retardant additive. The following examples are provided for the purpose of explaining the present invention in more detail, and are not intended to limit the disclosed invention. Unless otherwise stated,
All parts are parts by weight, weight in grams, temperature in degrees Celsius, and volume in milliliters. Example 1 10 grams (0.025 mol) of tetrabromobisphenol A136 was dissolved in 100 ml of dimethylformamide and charged into a 500 ml four-necked flask equipped with a stir bar, thermometer, condenser, dropping funnel and heating device. To this solution was added 2.65 g (0.025 mole) of soda carbonate maintained at about 60 to about 80°C, causing a vigorous reaction. Next, 21.9 grams of 1-(2,4,6-tribromophenoxy)-2-bromoethane (0.05
A solution of 21.9 g (mol) in 100 ml dimethylformamide was added dropwise to the reaction mixture. The temperature of the reaction mixture when the addition of this solution begins is
It was 98℃. The reaction mixture was heated to 100℃ for about 3 hours.
heated to. Add about 300ml of water to the reaction mixture,
The liquid in the reaction flask was decanted. Methanol was added to the reaction flask and mixed with the reaction mixture. A material with a melting point of about 136-150°C was obtained. This material was recrystallized from a benzene/methanol mixture. 16 g of material with a melting point of 149-151°C were obtained. Example 2 Tetrabromobisphenol A163.2 was added to 3 flasks equipped with a stir bar, condenser, and thermometer.
g, 31.8 g of soda carbonate, and 1000 ml of propylene glycol. The reaction mixture was heated to 100° C. to form the disodium salt of bisphenol A. Add 262.3 g of 1-(2,4,6-tribromophenoxy)-2-bromoethane to this reaction mixture.
was added. The reaction mixture was then heated to 140°C. This was subsequently cooled, water was added and the mixture was filtered off with suction. The resulting solid was dissolved in benzene and then the benzene solvent was evaporated. The solid thus obtained was placed in a mixer and the product was ground into a fine white powder while slurrying with acetone. The white powder was removed from the solvent by suction and dried in an oven. 293.4 g of product was obtained, with a yield of 77.7%. The product had a melting point of 157-159°C and a bromine content of 66.11%. Example 3 Tetrabromobisphenol A136/10g
(0.025 mol) and 2.65 g (0.025 mol) of soda carbonate.
The resulting solution in 100 ml of dimethyl sulfoxide was charged to a 500 ml four-necked flask equipped with a stir bar, thermometer, condenser, dropping funnel and heating device. A mixture of 100 ml of dimethyl sulfoxide and 1-(2,4,6-tribromophenoxy)-2-bromoethane was then added to the reaction mixture. The reaction mixture was then held at about 110°C for about 3 hours. The reaction mixture was cooled and water was added to it. The reaction mixture was filtered with suction to obtain a crude solid having a melting point of about 135 to about 140°C. The crude solid was washed with hot acetone, filtered off with suction and dried. Melting point is 156 to 158
Bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol-A ether at °C
Obtained 24g. The yield was 76%. This material contained 61.65% bromine. Thermogravimetric analysis of this material revealed that 25% of its weight at 377℃
%, lost 50% of its weight at 387°C, and lost 75% of its weight at 395°C. Example 4 54.5 g of tetrabromobisphenol A, 10.6 g of soda carbonate, and 300 ml of propylene glycol were charged into a four-neck flask equipped with a condenser, a thermometer, a stirring rod, and a heating device. mixture
Heating to 100°C produced a clear light yellow solution indicating the presence of the sodium salt of bisphenol A.
To this reaction mixture was added 125.8 g of 1-(2,4,6-tribromophenoxy)2-bromoethane.
The reaction mixture was heated to 140-150°C for about 3 hours.
The reaction mixture was then cooled to 40°C. After adding 500 ml of water to the reaction mixture, it was filtered, and the formed solid was washed with acetone, collected, ground, mixed with acetone, and filtered again. The product obtained by refiltration was then dried. The product weighs 97.2 g, has a melting point of 157-159°C, and has a yield of 77.
It was %. When this substance was subjected to thermogravimetric analysis, it did not lose 25% of its weight at 373℃, but at 387℃.
50% of its weight at 394℃, 75% at 394℃
I lost %. Manufacturing Example 5 of ABS Composition Bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A was added to black ABS resin BorgWarner “GSM-” manufactured by BorgWarner.
4500 [Borg-Warner “GSM4500”] (product name)
An acrylonitrile-butadiene-styrene composition was made by adding it to the dryer at 180°C for 240 minutes. The above aryl ether can be prepared using a Brabender prep center mixer (Brabender).
Instrument Inc. [C.
W. Brabender Instruments, Inc., South
[Hackensack, NJ] weighing head model R6) and mixed with ABS. The mixer is equipped with a pair of roller-type vanes positioned at a head with a heat transfer device. The whole mixture is about 220
It was heated to ℃ and became molten at this temperature. The formulation was removed from the mixer, cooled and crushed into chips. The chips were then molded into a 1-ounce Newbury injection molding machine model HI-30RS (manufactured by Newbury Industries, Inc., Newbury, Ohio).
injection molded. A 60 second molding cycle was performed with a ram pressure of 2000 p.si. After heating and melting these chips, they were injected into molds to produce solid samples for testing. The Izot impact strength and heat distortion temperature (unannealed) of the injection molded samples were measured. A flammability test was also conducted in accordance with Underwriter's (insurance company) test item No. 94 (Flammability test method for plastic materials, UL.94. February 1, 1974). For this test, the specimen was held in the clamps of the annular support so that the longest dimension was vertical and the lower end of the specimen was 3/8" (0.95 cm) above the upper end of the burner tube. The upper edge of the specimen was supported. The burner was then ignited away from the specimen and adjusted to produce a 3/4 inch (1.9 cm) high blue flame. The test burner flame was placed at the lower edge of the specimen. Place it so that it is in the center of
Hold in this position for 10 seconds. Next, the duration of flaming combustion and cauterizing combustion of the test piece was examined, excluding the test flame. If the flaming combustion or cauterizing combustion of the test piece stopped within 30 seconds after the test flame was removed, the test flame was placed again under the test piece immediately after the stop and was held for 10 seconds. Remove the test flame again and check the duration of flaming combustion or cauterizing combustion of the test piece. If dripping of flaming particles or droplets occurs during combustion in this test, the drippings should be placed 1 foot (30.5 cm) above the test piece.
Drop onto a horizontal cotton fiber (untreated surgical cotton cloth) placed below. It is believed that highly flammable particles can ignite cotton fibers. The duration of flame generation or ablation after application of a test flame for a vertically mounted test specimen is (5 times with 10 flame applications)
The test specimen outside the clamp must not burn out completely during the test. Materials that meet the above requirements and do not cause flaming particles or liquid drips during the combustion test are classified as "-1". Materials that meet the above requirements but produce flaming particles or droplets that combust briefly during the test are classified as "-2". Under the specified conditions, materials with an average duration of flaming combustion or cauterizing combustion of less than 5 seconds are rated "-0". Example 6 The method described in Example 5 was carried out in substantially the same manner except that Marbon's ABS resin "GSM-4500" (trade name) was used as the resin. The concentration of the retardant was 22% and the concentration of antimony trioxide in the composition was 4.4%.Brabender Plasticorder (CW Brabender Instruments, Inc.). ，South
The mixture was kneaded at 220° C. for 120 seconds at 100 revolutions per second on a model PL-V150 (with a pair of roller blades, manufactured by Hackensack, NJ). The resin was first melted, the flame retardant and antimony trioxide were added to the resin, and the mixture was melted for 2 minutes. This crushed product was then compression molded into two 3.25 inch x 1/8 inch (8.125 cm x 0.32 cm) broach-shaped specimens and one
5.0" x 5.5" x 1/8" (12.7cm x
A broach-shaped test piece measuring 14 cm x 0.32 cm was prepared.
Compression molding was carried out at 210° C. and a pressure of 20 tons for 5 minutes. Flammability test specimens were cut from appropriate broaches and measured using the method of Example 5. The flammability of the composition of the present invention is V-0 at UL941/8″ rating, U.L94
It was V-0 at 1/16" rating. Other Comparative Manufacturing Example of Flame Retardant Base Material 7 By almost the same method as in Example 5, 1,
2-bis(2,6-dibromo-4-t-butylphenoxy)ethane 21.2% by weight and antimony trioxide
4.4% by weight and Cycolac GSM4500 (product name: black ABS resin) manufactured by BorgWarner.
mixed in. The unannealed heat distortion temperature of this composition is
155〓(68.5℃): UL941/8″ rating is HB; U.B94
The 1/16" rating was HB. The 1,2-bis(2,6-dibromo-4-t-butylphenoxy)ethane contained approximately 51.5% bromine, and the bromine content was the same as the aryl of Example 5. The flame retardant effect in ABS was unexpectedly greater than that of the present compound. Example 8 In almost the same manner as described in Example 5. , bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A of Example 3
Acrylonitrile-butadiene-styrene with ether at a concentration of 19% (wt% relative to total composition) with antimony trioxide 3.76% (wt% relative to total composition) and chlorinated polyethylene at 3.23% (wt% relative to total composition) mixed in. The injection molded sample has an Izot impact strength of 2.08 footbond/inch (notched) and an unannealed heat distortion temperature of
164〓(73.3℃), UL941/8″ rating is V-0, U.
L.941/16″ rating was V-0; melting index was 8.2 g/10 min at 220°C with a load of 5 kg. Comparative Example 9 Mechanical stirrer, Claisen type Y
Mold adapter, condenser, graduated dropper, thermometer, Thermowatch (product name)
equipment, and tetrabromobisphenol A217.4 in two three-necked round-bottomed flasks with heating jackets.
(0.40 mol) and 306.7 g of ethylene glycol monomethyl ether (methyl cellosolve) to prepare a solution. carbonate of soda while stirring the solution.
42.4 g (0.40 mol) was added and the contents of the flask were heated to 120°C. Ethylene dibromide (EDB)
A solution of 64 g (0.34 mol) dissolved in 207.6 g of methyl cellosolve was added to the reactor to form a reaction mixture.
It was heated to 120° C. with vigorous stirring for 4 hours. Then add 1-bromo-2 to the stirred reaction mixture.
(2,4,6-tribromophenoxy)ethane
49.9 g (0.114 mol) was added rapidly as a powdered solid and the reaction mixture was heated to reflux to this temperature.
It was held for 4 hours. The reaction mixture was allowed to cool overnight and a solid precipitated. This was slurried with the supernatant liquid and the mixture was poured into 1000 ml of water with stirring. The white precipitate was separated from the mother liquor and washed with water and then methanol. This was first dried in a forced hot air oven at 60 to 65°C for 16 hours and then further dried at 60°C under vacuum at 20 inches (50.8 cm) of mercury for 3 hours. 2,
Ethylene dibromide and tetrabromobisphenol A having a 4,6-tribromophenoxy group at the end
A total of 246.9 g of oligomers were isolated. The organic bromine content of the product was 57.79%. Its softening range was 183 to 205°C. Thermogravimetric analysis of the product at a heating rate of 20°C per minute in a nitrogen atmosphere resulted in 1% by weight at 271°C, 5% by weight at 370°C, 10% by weight at 380°C, and 50% by weight at 390°C. , a weight loss of 75% by weight was observed at 426°C. Gel permeation chromatography analysis using polystyrene as a reference material revealed that this oligomer is a polymer with a typical bell-shaped molecular weight distribution ranging from about 900 to 5000 g per mole, with the majority of molecular weights ranging from 1300 to 2500. It became clear that the distribution was between. This compound is disclosed as a second preferred compound on page 3, column 1 of Japanese Patent No. 5173548, and corresponds to a compound in which the value of q is mainly in the range of about 1 to 3. Ta. In much the same manner as described in Example 5, the product of this comparative example was prepared at a concentration of 19% by weight (based on the weight of the total composition) and 3.76% by weight (based on the weight of the total composition). Antimony oxide and 3.23% by weight
of the acrylonitrile-butadiene-styrene resin along with chlorinated polyethylene (of the total composition). The injection molded specimen has an Izot impact strength of 0.6 ft lb/in (notched), an unannealed heat deflection temperature of 172〓 (78°C), a UL941/8″ rating of V-0, and a UL941/16 rating of V-0. , or the melting index at 5Kg load is 2.6g/10 minutes, 220℃
It was hot. Comparative example 10 Mechanical stirrer, Claisen type Y adapter,
17.4 g of Tetrabromobisphenol A in a 2-well, 3-neck, round-bottomed flask equipped with a condenser graduated dropping funnel, a thermometer, a “Therowatch” device, and a heating jacket.
(0.40 mol) and 306.7 g of methyl cellosolve were charged. 42.4 g (0.40 mol) of sodium carbonate was added to the solution produced by stirring the mixture, and the reaction mixture was heated to 120° C. while stirring. A solution of 90.2 g (0.48 mol) of ethylene dibromide dissolved in 207.6 g of methyl cellosolve was added and the resulting entire reactor contents were heated at 120° C. for 4 hours with mechanical stirring.
Heated. Next, 39.2 g (0.118 mol) of 2,4,6-tribromophenol and 9.4 g (0.089 mol) of sodium carbonate were added to the hot reaction mixture. The reaction mixture was then heated to reflux with stirring and brought to this temperature.
After holding for 4 hours, it was cooled for about 16 hours. The generated precipitate was slurried with the supernatant liquid, filtered, washed with water, and finally washed with methanol. The precipitate was dried initially in a forced draft oven at 60°C for 16 hours and then in a vacuum oven under a vacuum of 29 inches of mercury at 60°C for 3 hours. Its organic bromine content is 52.10%
The softening temperature range was 197 to 244°C. The temperatures at which weight is reduced by 1, 5, 10, 25, 50 and 75% in thermogravimetric analysis performed in nitrogen at a heating rate of 20°C per minute are 113, 379, 388, 397, respectively.
The temperature was 401,426℃. As a result of gel permeation chromatography of oligomers using polystyrene as a standard,
The product was found to have a broad molecular weight distribution from about 1,200 to 30,000 g/mol, with the majority of the polymer having a molecular weight in the range of about 1,600 to 8,700.
This compound is described in Japanese Patent No. 5173548.
The value of q disclosed in the first column of the page is mainly about 7.
This corresponds to 10 to 10 compounds. In much the same manner as described in Example 5, the product of this example was added to 3.76% by weight of antimony trioxide at a concentration of 19% by weight (based on the total composition).
(for all compositions) and chlorinated polyethylene
It was incorporated into the acrylonitrile-butadiene-styrene resin with 3.23% by weight (based on the total composition). The Izot impact strength of the injection molded sample is
0.84 ft-lb/in (notched), unannealed heat distortion temperature 173〓 (78.5°C), UL941/8
Rating is V-0, UL941/6″ rating is V-0, 5Kg
The melting index at 220° C. under a load of 0.8 g/10 min. Table 1 summarizes the results of Example 8 and Comparative Examples 9 and 10, and shows that the composition of the present invention has extremely high compatibility with the flame retardant compound in ABS resin, and that the composition according to the prior art It has been revealed that the impact resistance is significantly improved compared to that of conventional materials.

[Table] Example 11 In almost the same manner as in Example 8, bis(2,4,6-tribromophenoxyethyl)tetrabromobisphenol A ether of Example 3 was added at 20% (by weight based on the total composition). %) and 4.5% antimony trioxide (% by weight of the total composition). Comparative Example 12 In a reactor equipped with a condenser and a stirring device, tetrabromobisphenol A (13.6 g, 0.025 mol)
and 2,4,6-tribromophenyl chloroformate (19.7 g, 0.05 mol) were dissolved in benzene,
Pyridine (6 ml) was added dropwise. The solution was stirred at room temperature for 2 hours and the solid formed was filtered and washed with water. The crude product obtained was digested in boiling methanol for 15 minutes, filtered after cooling, and 20.0 g of the product isopropylidene (2,6-dibromo-p-phenylene) bis( 2,4,6-tribromophenyl) carbonate was obtained. As a result of analysis, the Br content was 62.8%. Comparative Example 13 Obtained by reacting tetrabromobisphenol A and propionic anhydride in propionic acid
CN-482 (Chemische
The experiment was carried out using the Fabrik kalk (manufactured by Fabrik kalk). The reaction formula is as follows. CN-482 is a white powder with a molecular weight of 656 and a melting point of 108-111°C. As a result of analysis, Br content is 48.3%
It was hot. In the same manner as in Example 8, CN-482
antimony trioxide at a concentration of 22% (wt% relative to the total composition) and 5.0% (wt% relative to the total composition)
I conducted an experiment as The compositions obtained in Example 10 and Comparative Examples 11 and 12 were injection molded in the same manner as in Example 5, except that GSM-1000 (ABS resin) was used instead of GSM-4500. The obtained samples were subjected to an Izod impact test and a combustion test. The results are shown in Table 2.

[Table] From the results shown in Table 2, the composition containing a compound bonded by an ether bond according to the present invention maintains flame retardancy equivalent to that of a composition containing a compound bonded by a conventional ester bond. However, it can be seen that the impact resistance is improved. The above embodiments are provided to illustrate the invention and are not intended to be limiting. Many other variations and modifications will suggest themselves to those skilled in the art. These are to be considered within the scope of this invention.

[Claims]

1 It is characterized by comprising as main components a synthetic resin emulsion or suspension (A) and a phenol resin powder (B), and the solid content weight ratio of both components is 100:5 to 500. synthetic resin composition (provided that the solid content weight ratio of both components (A) and (B) is
Except for plywood adhesive compositions that are 10/90 to 90/10. ).